Purification of organic solids



Aug. 20, 1935.

s. P. MILLER 2,011,724

PURIFICATION OF ORGANIC SOLIDS Filed oct. 2S, 1932 ATTORNEY ffii tutti Pommern-N or ORGANIC; somos stuart r.'Miiier,.Eng1em0s,N. J., assignor to The 'BarrettiCompan New York, N. Y., a corporation4 of' New Jersey Application october 2s, ieagfserial Notcsasies sciame. V(ciazsoirce) My invention relates Vto. theA .purification or `treatment of materials Aand particularly tothe purication of materials `by' the selective action cfa: solvent which isvnorrnallyI gaseous, or has a high vapor tension. at' ordinary temperatures.

glVlyinventionA isadapted for use, inl general, for ,treating `or purifying materials but. ,is particularly adapted for the puricationpf crude anthracene; ...Crude anthracena. such as that de- It has been proposed-heretoforeto` purify anthracene by the' actionoi-liquid anhydrous ammonia. However, in carrying out the process,I it has not been possible' to remove ythe-'ammonia cormolete'lyl from' the Lextractedf materialA and `from i the apparatus Ain which 'the' processf is-l practiced.

.This hasfresulted' in substantial` lossof ammonia and consequent increase in cost of .thefpuricatiem/and has hadfthev further disadvantage that on: removal. of the extracted: anthracene from the apparatus;. large amountsof ammonia.- gas are evolved, making the operation difcultfto `carry out. Residual ammonia Will Ybe.v evolved `from the .Y extracted anthraceney-making .its handling and storage diicult. 4

have discovered that substantially pure, dry

lanthracene of highilcommercial'value canV be obtained without the loss of ,ammonia and without the' attendant: nuisance of' strong *ammonia fumes extracting crude anthracene with liquid' amfmonia: in; a closedA system; and thereafter treating j the purified anthraceneA t-o` remove `ammonia `adhering thereto prior'to. 'exposing the purified: anthracene to the atmosphere. `Substantially pure anthracene, free from-ammonia, is thus obtained and.' ammonia removed trom'the anthracene-is y recovered fory re-user inr thefprocess.

)Among the-objects of my invention are to pro.- vi'defanewv andi improved method of purifying.. materials, such asy anthracene.. whereby .a substantia'lly pure, -dryi cormnerciallyV valuable product is obtained; .to recover and conserve` solvent used in the process; to separate-andnrecoverimpurities removed from` anthracene; or ,the like l'bythe solvent; and `tot' provide'simple vandimprovedjap.-

params:for;carryinggoutatlrieprocess..u These and other-objects and featuresof my invention Will appear'from the following description thereof in which reference is madeto the accompanying figuresr of the drawing, in Whichn Fig. lillustrates a. preferred type of apparatus forrpracticing my process, and i Eigs. `2 and 3f illustrate diagrammatically modicati'ons' of a portion of4 the apparatus illustrated -in Fig., l.

This inventionis notonly applicable to the purification of anthracene by extraction with liquid ammonia, but. to-A purication of i anthracene and other organic solids, for example fluorene, by extraction with other extracting media, such for example as sulphur dioxide,.aqua ammonia containing: at least 75lvper centfammonia in solution, methyl andi ethyl .fethers (CHaOCI-Is and CzIrIsOCzI-Is),v acetone (CHaCOCl-Is) and the like. For example, crudel anthracene may be puriiied in accordance withl this invention by extraction with acetone insteadof with ammonia as described below, higher temperatures or lower pressures, or both,4 being employed as required by the higher boiling. pointfacetone. Acetone has a boiling point .of I56:.5o C. and a melting point of -94.6 C. Its vapor; pressure at 209C. isv 180 mm. of mercury; at 40 C., 440 mm. ot` mercury; at 56.5 C., 760 mno. of mercury;. at 60 C., 860 mm. of mercury; and at 80C., 1611 mm. ofmercury. Using acetone `as the extracting.l medium, it is preferred to mainltain in theextractor a pressure of about atmos- .pheric or `somewhat above atmospheric, for example pounds. .Y v

`In accordance .Withmy invention, crude an- Vthracene` containingsay to 40 per cent of anthracene, is` introduced into an extractor adapted to-be placedunder. suicient pressure .to` retain -the ammoniain liquidform at normal atmosphericV temperature or at the temperature at whichthefprocess is carried out.` "Ifhe extractor is'then: sealedand is preferably evacuated to remove air therefrom. Liquid ammonia from a reservoir isthen introduced into the extractor in.;contact with .the `antl'iracene. The solvent actionot liquid ammonia on the impurities in anthraceneis considerably greater When operating at temperatures iny the neighborhood of atmospheric temperature or higher and' under superatmospheric p pressure than When operating under atmospheric. `or `lovver pressures and at very lovvV temperatures.. ,For this reason the ex-l tractor is preferablymaintained during operationr1 under. suitablepressure: to insure the maintenance ci theammoniain the extractor, in liquid formattheadesi'red temperature of extraction,

e. g. tos50 C. When operating under normal atmospheric temperatures this pressure will ordinarily be about 100 pounds per square inch or somewhat higher, e. g., 125 pounds per square inch. f

The liquid' ammonia may be introduced either n s or otherWisejto-aid'in the evaporation of the continuously or intermittently into the extractor in contact with the crude anthracene-allowing i the ammoniarto vcollect therein until the liquid has reached a predetermined level. When operating intermittently the ammonia collects in the extractor'until the anthracene is completely I i ties Yin liquid ammonia and this property of the immersed therein; Thereafter-thehliquid ammonia containing impurities isthen discharged fromlthe'extractor by meansof a siphonnror otherwise.` Complete immersion of the anthacene y in theliquid ammonia insures thorough contact o1" all particles of anthracene vwith the liquid' ammonia and substantially complete `extraction of soluble limpurities therefrom. Channeling through the solid material, which would be oc-V casioned by thejcontinuous vpassage of? liquid ammonia therethrough, does not occur when operating as herein disclosed.' After thedischarge of liquid'ammoniaffrom the anthracene, addi- .tional liquid .ammonia may be fed tothe anthracene which'is again completely immersed, and

the" vammoniacontaining impurities 'withdrawn upon complete immersion of theanthracene.

These cycles^are repeated severall times until 'A the anthracene is Vpurified to the desiredv extent.v

i The liquid ammonia and solid anthracenermay be agitated inthe extractor `whereby impurities,

such as phenanthrene, fcarb'a'zol, etc., are more readily dissolvedand the resulting solution' 'of the impurities in liquid ammoniay is withdrawnV from the anthracene. The solutioni thus obf tained'is passed'to a receptacle wherein the amvanother receptacle Awhile distilling ammonia from the solution first obtained )After the anthracene has been treated with ythe solvent to removethe desiredlamount of impurities therefrom and after the liquid ammonia has beenwithdrawn fromfthe` anthracene, ammonia remaining in vcontact with kthe anthracene is expelled therefrom and recovered for-reuse in n thev operation., The removalr of ammoniav from 'the anthracene may be effected by heatingthe anthracene to a sufficienttemperature to evapo-` rate the ammonia under? the pressure maintained in the system, or if preferred,steam,air or other 'inert ga's'may be-V blown throughy or over the anthracene to expel ammonia remaining therein'. Dry air preferably employed when it isdesired to condense" the ammonia and thus remove it liromthe air leaving theanthracene containing residual ammoniaf' The ammonia `gas thusv removed from the anthracene may be condensed or may be absorbed in a' suitable n'laterial, such as water ork sulfuric 'acid'. 'e When steam isl employed, the mixtureof steam and ammonia may be ycooled toi condense the majorportion ofthe water`, and the ammonia vaporspassed through Aa drier, containing calcium'olxide orroth'er sutable drying agent, priorvfto' condensing' and reusing the same. The waterncontaininglsome dissolved ammonia condensed from the mixture offst'eam and ammonia in the latter operation y separation and recovery thereof.

may be heated to produce steam for further treating the purified anthracene'. It preferred, the ammonia remaining in contact with the anthracene may be removed 4by evacuating the lextractor in which the anthracene is containedA while heating the anthracene bymeans of` steam impurities is'utilized in my process ior `effecting v The phenanthrene `and other hydrocarbons are more readily soluble in liquid ammonia than is carbazol. Therefore, the liquid ammonia first passed in contact with the crude anthracene contains prolhydrocarbons than the liquid ammoniav subsequently 'passed in contact withithe anthracene'. When operating in either a continuous or intermittentbycle, I" prefer to 'separate that portion of the liquid ammonia virst withdrawn from the anthracene and thereafter vto. collect separately that portion of the liquidarnmonia subsequently passedin contact with theanthracene whereby a rough separation of the phenanthrene and hydrocarbonsf from the carbazol is effected. The

fractions Vofthe liquid ammonia thus separated may betr'eated independently for effectingthe recovery ofconstituents'of the impurities therefrom. The liquid ammonia thus removed from `the anthracene inthe initial stages of the process contains themajor portion of the phenanthrene and other,` hydrocarbons and is collected in one or'more receivers separate from those in which ammonia containing carbazol': and impurities subsequently' removed fromr the anthraceneby further extraction thereof isfcollected.

The 'ammonia is distilled off or o-therwiseseparated fromthe impurities in the various receivers, andr in order to avoid solidication of the impurities 'in the receptacle, I preferto introduce a solvent for the impurities into the receptacles prior to or-during ldistillation of the ammonia so that the.l impurities are prevented from solidifyingorcrystallizing koutof 'the solution onto the `-heating coils and walls of the receptacle."v This treatmentffacilitatesthe removal ofimpurities from 'the receptacles. j However, if preferred,

solvent for the impurities may be vintroduced into vimpurities therein prior to subjectingfanthracene to treatment with liquid` ammonia or other solvent ycomposed of a normally gaseous substance in liquid form. 'I'he anthracene treated Ain accordance with my process is referred to throughout the specication and in thev claims as crude anthracene. However, it is intended that the term4 crude ,anthraceneas used shall include' anthracenewhichhas been given a preliminary treatment to remove a portion of the impurities therefromjas Well as anthracene which has not Crude'anthracene containing from 25 to 40 per cent of kpure anthraoene'whentreated in accordance with my`process Vas heretofore described, 4is

' diameter than pipe 6, to the receptacles 32 and anima-1 janthracen'e to be ytreated `is introducedinto an yextractor 2 yadapted to receive and contain liquid "ammonia from the ammonia reservoir "4 through 'the pipe 6 coninolledby the valve 8,.l supportingscreen, spaced from the bottom of the extractor, supports `the solid anthracene and is provided with apertures of sulicient neness to prevent the anthracene from passing therethrough.

The extractor may be provided with astirring device lll carried"- by the shaft `I2 extending ithrough a packing I4 in the cover of the extractor and adapted to be rotated by the motor I6 Iand worm gear I8. A liquid level indicator 20 and` tractor is surrounded by a steam jacket 24 and in addition theextractor may be provided with a centrally located `member .26, as shown inflig.v 3,

. into which steamis passed for aiding inthe heating and removalof ammoniar from the solid matefrial.

Liquid ammonia containing dissolved limpurities is passed from thejbottom of the extractor throughthe pipe 36, of somewhat greater internal 34. Only two receptacles for receiving the liquid ammonia and dissolved impurities are shown although it will be understood that any suitable y the extractor and serving as a means for periodjes.

lic'ally discharging liquid ammonia and dissolved impurities from the extractor when `the apparatus is voperated intermittently. However, a bypass 38, controlled by valve 46, extends across the bottom of the Siphon 36 to enable theapparatus tobe used'forxthe continuous removal ofliquid ammonia and impurities from the extractor, if so ried out `either continuously or intermittentlyy and liquid ammonia containing dissolved impurities withdrawn from the extractor and passed into either of the receptacles 32 and 34.

'The receptacles32 and 34 are each' provided with a steam jacket 52 for heating and distilling I theammonia contained therein to drive 01T the ammonia and recover the dissolved impurities.

The receptacles may also contain steam coils 54 for ,aiding in the `distillation of the ammonia.

'Ammonia gas. produced by distillation off ammonia in the receptacles is removed therefrom Athrough the pipes 56 and58. controllediby valves `6i! ,and-62 and connected with. vapor line 64 lead- Ammonia gas 4.expelled from .the .puriled.anthra cene 1in zthenextractorfZ is also :passed to theammonia rreturn line 614 :by means ofthe pipe 'l0 controlledbyvalve 12. l

A vacuum pumpf1l4connectedto the vapor line .64lat 7,5 serves to evacuate the extractor .and receptaclesprior `to the introduction of liquid am- `fmonia :into thesystem. The vacuum pump may also be usedfor removingbammonia gas from the extractor andreceptaclesto return the sameto l other parts .of the system. IThe pipe 16 leading y frornthe vapor line 64 to the vacuum pump 114 isprovidedl withv a valve 'I8 ^for closingo this por- 4tflonoi theapparatus during the extraction operation. vThe dischargeside of the vacuum pump is provided with an Yexhaust 80 controlled by valve 4:82, and is also connected to the vline 64-serving to returnammonialgas .to 'the vapor line `64 when using thewvacuum pump `forremoving ammonia from' the extractor crthe receptacles 32 and 34. `A\ valve 86 is located inthe vapor'` line64 `below condenser 66 yand serves to maintain the vacuum in the extractorand .the necessary pressure inthe condenser and liquid ammonia receiver during the evacuation stage. 11A valve 88is also inserted in the lline64 to cut off the vacuum pump when it is notbe'ing used. For practical purposes, a multiple stage vacuum -pump may be used of any desired and .well known' type.

In .operating the apparatus Vshown in Fig. 1, crude anthracene to be purified is introduced into. the extractor l2. The extractor is closed and valve '12in pipe 10 and valves E0 and 62 in p1pesf56 and 58- leadingfrom the receptacles 32 and `34 respectively are opened. Valve 86 in the vapor line 64V andV valve 88 in the pipe `84 Jare closed. Valve 13 inthe pipe 161eading 'from the vapor line to the vacuumpump is opened `and vvalve 32"in the exhaust .80 leading to the atmosphere is opened. Thevacuum pump `14 is then operated to withdrawfair'from the extractor and receptacles as well as the piping `communicating therewith untilsubstantiallyall .off the air has been removed from thesystem. Valves 12,118,` and 82 are` then closed. 'Liquid ammoniazis discharged from 'the reservoir 4 into Vthe extractor' 2 byfopening the valve v8 in the pipe 6 and the stirring device I0 inthe` ex- :tractor is operatedtov agitate the anthracene and liquid. ammonia during operation. As soon Las `pressure is builtv up in extractor 2 and receivers'32 and 34, valve 86 is opened to admit vapor'totthe condenser 68 and heat is applied toone of the receivers 32 and 34. If` intermittent .discharge ofthe liquid'ammonia containing dissolved impurities from the extractor is desired, the valve 4u in the by-.pass 38 is closed and the level `of the liquid ammonia l in the extractor rises'as ammoniacontinues `to flow through the `pipe v6, until the level thereof is at or above the "top of the siphon 36 inthe pipe 30. Ammonia .then .owsfthrough the siphon 36 and iiow `thereof continues at a rate greater than the rate `of feed through pipe 6 until all or substantially ally ofthe liquid ammonia in the extractoris withdrawn `therefrom and the Siphon broken. Liquid ammonia continues to collect in the extractor again `until the siphon hasagain been estabiished. 1n this Way intermittent suing and 4discharge tofv the extractor is eiected. If conrtinuous removal of the liquid ammonia from the extractor is desired, the valve 40 in theby-pass i312: is opened and liquidammonia is withdrawn Acontinuously fromthe4 extractor, preferably at ing to the Acondenser-166 located in the .tank 68. a rate `equal t'oftl'iatl at which' ammonia-is"in 75 tro`duced`i.into thei extractor: so as to .maintain a.-v continuous v:supply .of I liquid. ammonia.A in` the extractor while continuously withdrawing'liquid 4ammonia containing impurities. therefrom: ,.l 1.2

'.When withdrawing liquid .ammonia vvfrom1tl1e extractorj eitheraoontinuously or intermittently, the 'ammonia containing dissolved.. impuritiesr passesy through :the lower .portion vl2 of .the .pipe y3l). tooneof the receptacles 32:and*3!l.zv 'Ihe Nalves .48. and i). inthe ,pipeslland v46 yare adjusted'to de1iver.-.the-liqudamInQniaLto whichf y. 'everof. the .receptaclesy 32j and 3,4 it is desired toi-lll. ,'Thegoperationthus continuesfuntil one' .receptacle -isfilled or"y until.; the major portion I of the i. phenanthrene.. and i other soluble. vvim f the vacuum pump 14.

purities have. vloeenextractedfrom the anthracene. If rtheliquidammonia withdrawn from,y the` extractoris being -passedflrtof. receptacle' 32 and the valve 43r is open, the rvali/e5() in the pipe ,125 is closed. .Thereafter,;fwhen. the receptacle 32 is full' orthema-j or .portion of the phenanthrene andotheraimpurities have been extracted yfrom the anthracene,y `the valve-481s.. .closedand valve 5G `opened .l whereby-liquidi ammonia .containing impurities is passed-tothe receptaclell;` A1 f f As liquid ammonia withdrawnr from the 'extractorjcontinues to pass into the. receptacle 34,

"kept openduring theextraction.v In this way `theammonia in one. ofthe receptacles is dis'- tilled while liquid ammonia from j thexextraotor isgbeing collected .y in Vthe other receptacle. g The ammonia gas .passed-tothe vvaporfline .64 yflows upwardlyto thecondenser 66 in which itis. cooled and; liquefied` and returned to the liquid am- -:monia'reservoir4.A

'f ',.Iy mayiintroduce into the.k `receptacles S2-.Land `311' asolvent vfor the impurities to .dissolve the same and prevent ycrystallization, .thereof on the `walls and heating icoils. within ythe chamber as *distillation proceeds. .Thesolvent. used;.should be substantiallyynonevolatile.V underthe conditions under which:` distillation inthe receptacles .takesplace in-order to .obtain substantially pure `arnmoniagas .as a distillate.) TheA solvent may .be acoal tar oil, such as, creosote oil; press oil remaining ,after fthe' removal of .-'fnaphthalene f fi-om; a naphthalene 'fraction,..etc, @The solvent .and ydissolved phenanthrene, carbazol, .eto.` arev .periodically .or continuously removed and :fresh ysolvent introducedg-x- The solutions. ofnampurities inthe solvent removed from the receptacles'32 andv 34 may then be separately. treated to; recover Aphenanthrene ...and carbafzol therefrom. .'Iiheso- {lutions may be mixedfprio'r to separation ofthe phenanthrene and carba'zol. il-Io'wever; by. co1- leoting theammonia solution ,withdrawn from the extractor iny separate 'fractions in thev "manner y heretofore described sothat liquidammonia relatively lrich in I phenanthrene 'is g collected .inv y,one receptacleA and vliquid ammoniayrelatively rich in. carbazolgis collected in another receptacle,

Aan initial separation of lthe phenanthrene ,and

.carbazolis effected;

The, extraction of theanthraceneiis continued' :until the' .anthracene has beenpuried. andy impurities v'removed therefromjto thedesired. 'exytent The valvefwB in. the pipei is then'V closed t utoiftheowof liquid..ammonia tothe .extractoru Ammonia: containing; impurities fis with'drawn from the gextractonlthe valve 38 beingopenedfiif closed) tov permitadraining as .completely :as possible. After draining, valve andgvalyesf, 53.160 and 62am closed. Steam ispadmitted tothe steamwjacket v24 andto the i 01T from theqpuried anthracene and passed through the-pipe *lli tothe rvapor liney 64 andrecoveredv for refuse; .'Subsequently, j.valve 86 isV closed and valves'l-.andopened and additional ammonia vvapors withdrawn from the 'expt'ractorand, returned to the cycle by-meansof I 'Ihewvacuum thus applied to theextractor Zamayalso `be applied to the receptacles 32 andl Sllktoaid in the removal ofv ammonia therefromgitdesired fby opening valvesllvandZ'.

'o In the modified `from` of thevaaparatosl tuus.- trated inFig. `2 of the drawing, the ammonia reymainingin contactwith thepurified anthracene is expelled by passing steam, preferablyat. to 4 pounds pressure or aboveinto contact with the anthracene'toj vaporize. the ammonia therein. Fogrthis; purpose. steam is introduced .IlUO Vextractor through the steam inlet .89 in 'theibottom, thereof.: -Amixture comprising'steam and ammonia gas passes-out through; the steam outlet pipeSil inthe.topgof the extractor, yleaving the an'tllracenev in a pure condition." The mixture of rsteamfand'ammonia passes .toga condenser .93 .wherein the greater part ofthe 'steam is-con densedto'waten The condensate and-'ammonia vapors then pass to one or v.the other ofi-,collectors 94 and 96. y Ammo-nia vapors are withdrawnfrom collectors 94 andv 96 ,by.a, vacuum pumped and passed'` to a drying tower-lll@ lled withilime'or other suitable dehydrating agent. The `resulting dried 'ammonia gas may be passed to a condenser, .such as 65v `of Fig.l Land returnedto' the'cycle or maybe otherwise {recoveredand used. The con- -densate from condenser 93 is allowed to accumulate untilone collector 94` orti@ is full and then `the condensateisapassed tothe vother collector. The condensate constitutes a weak ammonia liquor.. 1 Itmay be heated byv steam coils lili and M12 to distillfo ammonia Avapors which are withdrawn v bythejvacuurn pumpg. o Distillation of the liquid inthe collectors 943i and llv may be employed to Y` blow. air'or. other inertgas through'the anthracene :and 'pass the resulting mixture Vof gases to a nchamber containing water, sulfuric acid or other .solvent for the ammonia. 1 When .the .ammonia is i absorbed in Water the ammoniacal liquor obtained .mayfbe'passed to collectors 94 and S6 rtobe treated "as-heretofore describeohving approximately. 35.5I percent anthracene, was Fintermittently immersed in liquid ammonia andr Athe .I ammonia r,drained therefronnf These cycles iwere .repeated thirteentimes. "A; relatively pure anthracene`v containinxf.;l 80.3 per ,cent ofy anthra- .cene'was obtainectf` In vanotherexamnle of this .n In on'eQexam'ple' of practicing this', invention, a

twenty-five. pound' chargeotav crude anthracene e traction from the distillationnf coal tar, containinvention, a 40 pound charge of crude anthracene containing approximately 37.5 per cent anthracene Was given thirty-six Washes with liquid ammonia and a relatively pure anthracene containing 8l per cent anthracene was thus obtained.

Since the free carbon? content of the crude is not removed by the ammonia Washv treatment, in

I order tov obtain a highly purified anthracene, it

is important to start with a crude low in free carbon, preferably co-ntaining less than 0.5 per cent o1" free carbon. For example, a crude containing per cent anthracene and l per cent free carbon, upon purification of the crude to 85 per cent anthracene will contain 3.4 percent free carbon a crude containing 3 per cent of free carbon Will contain 10.2 per cent in the purified product containing 85 per cent anthracene. The term free carbon is used in the sense common in the coal tar industry to indicate material contained in thebituminous compound which is insoluble in benzol or carbon bisulfide.

1 It is commonly determined as described by Weiss (Journal of Industrial and Engineering Chemistry, vol. 10, 1918, pages 736 and 820, Test D5) It comprises high-molecular Weight carbon compounds of low solubility, carbon, and other in` laqua ammonia, the pressure on the system may be k somewhat less than that required When using anhydrous ammonia and when using aqua ammonia the extraction of impurities is not so rapid and therefore the length of time of operation Will ordinarily be prolonged. When strong aqua ammonia is used, a certain amount of fractionation may take place, resulting in a deposition of Water in the receivers. This water may be Withdrawn with the impurities when emptying the receivers.

It will also be understood that the apparatus herei in shown and desciibed may be modiiied or other apparatus employed in carrying out the process without departing from my invention.

' 1. The process of producing purified anthracene products containing in excess of 80% anthra- 'cene by removing impurities from the anthracene by extracting the same With liquid ammonia, which comprises introducing crude anthracene material containing not more than about 40% anthracene and not more than about .5% free carbon into `an extraction Zone,` introducing successive charges'of liquid ammonia into Contact With said crude anthracene While maintaining a pressure in the extraction zone sufcient to maintain the ammonia in the liquid phase, removing` the major portion of each charge of liquid ammonia thus introduced together with dissolved impurities from the anthracene under treatment before contacting the anthracene with the next charge of liquid ammonia, repeating the successive contacts of said anthracene with liquid ammonia until the material in the extraction zone contains at least 80% anthracene on an ammonia free basis, adding to the liquid ammonia containing impurities removed from the anthracene a solvent for the impurities which solvent is substantially nonvolatile under the conditions under which distillation of the liquid ammonia containing impurities takes place, distilling the liquid ammonia solvent mixture to drive off the ammonia in vapor form and condensing and re-using the ammonia thus driven off.

2. The process as dened in claim 1 in which the anthracene material under treatment is agitated during the extraction thereof with liquid ammonia.

3. The process as defined in claim 1 in which the extraction Zone is evacuated after introduction of crude anthracene and residual ammonia remaining in the puried anthracene is removed in gaseous form, condensed and re-used.

4. The method of purifying crude anthracenev containing phenanthrene and carbazol, Whichcomprises extracting the anthracene with liquid ammonia under pressure, withdrawing the liquid anhydrous ammonia and dissolved impurities from the anthracene and separately collecting the liquid ammonia initially contacted with the anthracene which is rich in phenanthrene and the residual ammonia contacted With the anthracene which is rich in carbazol, separately recovering the phenanthrene and carbazol from the respective fractions containing the same, and removing residual ammonia from the puried anthracene.

5. The method of treating crude anthracene to separate impurities therefrom by the selective solvent action of liquid anhydrous ammonia contacted With anthracene in a closed system and under pressure which comprises evacuating the system to remove air therefrom, thereafter con# tinuously circulating liquid ammonia under pressure'in contact with the crude anthracene until soluble impurities therein have been removed to the desired extent, continuously separating liquid ammonia containing dissolved impurities from the anthracene, separately collecting that portion of the ammonia iirst Withdrawn fromthe anthracene, distilling off ammonia from the impurities dissolved therein While collecting that portion of the liquid ammonia thereafter Withdrawn from the anthracene, condensing the ammonia gas produced and returning the resulting liquid ammonia to the cycle, heating the anthracene after purification thereof and after the liquid ammonia has been Withdrawn therefrom to distill off ammonia remaining therein, and `recovering the ammonia gas thus produced.

STUART P. MILLER. 

